US20190207191A1 - Separator, Method For Preparing Separator And Electrochemical Device Containing Separator - Google Patents
Separator, Method For Preparing Separator And Electrochemical Device Containing Separator Download PDFInfo
- Publication number
- US20190207191A1 US20190207191A1 US16/211,526 US201816211526A US2019207191A1 US 20190207191 A1 US20190207191 A1 US 20190207191A1 US 201816211526 A US201816211526 A US 201816211526A US 2019207191 A1 US2019207191 A1 US 2019207191A1
- Authority
- US
- United States
- Prior art keywords
- separator
- substrate
- inorganic layer
- separator according
- fluoride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000758 substrate Substances 0.000 claims abstract description 119
- 239000011230 binding agent Substances 0.000 claims abstract description 16
- 239000011148 porous material Substances 0.000 claims description 41
- -1 magnesium nitride Chemical class 0.000 claims description 23
- 230000035699 permeability Effects 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 9
- 238000007740 vapor deposition Methods 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 7
- 238000010894 electron beam technology Methods 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 5
- 239000011777 magnesium Substances 0.000 claims description 5
- 238000002207 thermal evaporation Methods 0.000 claims description 5
- 239000002033 PVDF binder Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 238000000678 plasma activation Methods 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims description 2
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 238000000231 atomic layer deposition Methods 0.000 claims description 2
- OYLGJCQECKOTOL-UHFFFAOYSA-L barium fluoride Chemical compound [F-].[F-].[Ba+2] OYLGJCQECKOTOL-UHFFFAOYSA-L 0.000 claims description 2
- 229910001632 barium fluoride Inorganic materials 0.000 claims description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 claims description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000005240 physical vapour deposition Methods 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical compound [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 2
- AKJVMGQSGCSQBU-UHFFFAOYSA-N zinc azanidylidenezinc Chemical compound [Zn++].[N-]=[Zn].[N-]=[Zn] AKJVMGQSGCSQBU-UHFFFAOYSA-N 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 claims description 2
- 230000002349 favourable effect Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 96
- 230000006872 improvement Effects 0.000 description 22
- 238000012360 testing method Methods 0.000 description 20
- 150000002500 ions Chemical class 0.000 description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 239000002131 composite material Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 238000000151 deposition Methods 0.000 description 8
- 230000008021 deposition Effects 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229920000307 polymer substrate Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical compound [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000013077 target material Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- QDZRBIRIPNZRSG-UHFFFAOYSA-N titanium nitrate Chemical compound [O-][N+](=O)O[Ti](O[N+]([O-])=O)(O[N+]([O-])=O)O[N+]([O-])=O QDZRBIRIPNZRSG-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910000600 Ba alloy Inorganic materials 0.000 description 1
- 229910000882 Ca alloy Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- PZIBOVBPVADPBS-UHFFFAOYSA-J S(=O)(=O)([O-])[O-].[Si+4].S(=O)(=O)([O-])[O-] Chemical compound S(=O)(=O)([O-])[O-].[Si+4].S(=O)(=O)([O-])[O-] PZIBOVBPVADPBS-UHFFFAOYSA-J 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 229910001093 Zr alloy Inorganic materials 0.000 description 1
- PBZHKWVYRQRZQC-UHFFFAOYSA-N [Si+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Si+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PBZHKWVYRQRZQC-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- INNSZZHSFSFSGS-UHFFFAOYSA-N acetic acid;titanium Chemical compound [Ti].CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O INNSZZHSFSFSGS-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- HDYRYUINDGQKMC-UHFFFAOYSA-M acetyloxyaluminum;dihydrate Chemical compound O.O.CC(=O)O[Al] HDYRYUINDGQKMC-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 229940009827 aluminum acetate Drugs 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 description 1
- 239000001639 calcium acetate Substances 0.000 description 1
- 229960005147 calcium acetate Drugs 0.000 description 1
- 235000011092 calcium acetate Nutrition 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000005524 ceramic coating Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000005566 electron beam evaporation Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001659 ion-beam spectroscopy Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- JXJTWJYTKGINRZ-UHFFFAOYSA-J silicon(4+);tetraacetate Chemical compound [Si+4].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O JXJTWJYTKGINRZ-UHFFFAOYSA-J 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 1
Classifications
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- H01M2/1686—
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/0021—Reactive sputtering or evaporation
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/081—Oxides of aluminium, magnesium or beryllium
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
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- H01M2/145—
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- H01M2/1646—
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- H01M2/1653—
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/417—Polyolefins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/42—Acrylic resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/423—Polyamide resins
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
- H01M50/426—Fluorocarbon polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
- H01M50/429—Natural polymers
- H01M50/4295—Natural cotton, cellulose or wood
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
- H01M50/451—Separators, membranes or diaphragms characterised by the material having a layered structure comprising layers of only organic material and layers containing inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/491—Porosity
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
- H01M50/494—Tensile strength
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present disclosure relates to the field of energy storage and, in particular, relates to a separator, a method for preparing the separator and an electrochemical device containing the separator.
- the separator In the internal structure of the battery, the separator, as a key component, is usually a porous polymer film, which has the characteristics of electron isolation and ion conduction, and is used for normal transmission of ions between a positive electrode and a negative electrode without short circuit.
- a composite separator prepared by coating a ceramic coating layer on a surface of a polymer substrate has become a key technology to improve the safety performance of the battery. Forming an organic-inorganic composite coating layer by mixing inorganic particles and a binder can modify the surface of the polymer substrate.
- there are still some problems about such a composite separator that are needed for further research and development.
- the coating layer on the separator surface may easily occur cracks, aging, porosity changing, or detachment of ceramic particles and the like, thereby leading to deterioration of ion conduction performance and even cause security problems in severe cases.
- a first aspect of the present disclosure provides a separator.
- the separator includes a substrate with a porous structure and an inorganic layer arranged on at least one side of the substrate.
- the substrate is a porous substrate having a plurality of pores.
- the inorganic layer is a dielectric layer containing no binder.
- a thickness of the inorganic layer is 20 nm to 2000 nm, a mass of the inorganic layer is M1, a mass of the substrate is M2, and a mass ratio of the inorganic layer to the substrate M1/M2 is greater than or equal to 0.05 but smaller than or equal to 7.5, and an interfacial peeling force between the inorganic layer and the substrate is not smaller than 30 N/m.
- a second aspect of the present disclosure provides a method for preparing the separator of the first aspect.
- the method includes at least steps of: providing a substrate, which is a porous substrate having a plurality of pores; and forming an inorganic layer on a surface of the substrate and in the pores by means of vapor deposition, so as to obtain the separator.
- a third aspect of the present disclosure provides an electrochemical device including a positive electrode, a negative electrode, a separator, and electrolyte.
- the separator is the separator of the first aspect.
- the interfacial wettability and thermal shrinkage resistance performance of the separator can be effectively improved while the separator has a certain mechanical strength.
- the separator can have favorable mechanical strength and thermal shrinkage percentage while having high energy density.
- the inorganic layer is prevented from cracking and falling-off caused by the uneven distribution of the binder, and the problems of decrease of mechanical strength and blockage of pores caused by the falling-off can be alleviated, thereby improving safety performance and cycling life of the battery.
- a first aspect of the embodiments of the present disclosure provides a separator.
- the separator includes a substrate and an inorganic layer arranged on at least one side of the substrate.
- the substrate is a porous substrate having a plurality of pores.
- the inorganic layer is a dielectric layer containing no binder.
- the inorganic layer has a thickness of 20 nm to 2000 nm.
- a mass of the inorganic layer is M1, a mass of the substrate is M2, and a mass ratio of the inorganic layer to the substrate M1/M2 is greater than or equal to 0.05 but smaller than or equal to 7.5.
- An interfacial peeling force between the inorganic layer and the substrate is not smaller than 30 N/m.
- the ultra-thin inorganic layer since the ultra-thin inorganic layer is provided, the interfacial wettability and the thermal shrinkage resistance performance of the separator are effectively improved.
- the mass ratio of M1/M2 is in the range of 0.05 ⁇ 7.5, the separator has favorable mechanical strength and thermal shrinkage percentage while having high energy density.
- the hydrophilicity to the separator, thermal shrinkage resistance performance and mechanical strength of the separator are not further significantly improved.
- the inorganic layer on the surface of the separator may reduce the porosity of the inorganic layer on the surface of the separator, increase the ion transmission distance, and affect the rapid transmission of ions between the positive and negative electrodes, thereby causing deterioration of the dynamic properties of the cell.
- the problems such as cracking and falling-off of the inorganic layer due to the uneven distribution of the binder can be avoided, and the problems of mechanical strength reduction and pore blocking of the substrate caused by the falling-off that deteriorates the ion conductivity of the battery can be also avoided. Therefore, the safety performance and the cycling life of the battery can be further improved.
- an upper limit of a thickness of the inorganic layer can be 2000 nm, 1900 nm, 1800 nm, 1700 nm, 1600 nm, 1500 nm, 1400 nm, 1300 nm, 1200 nm, 1100 nm, 1000 nm, 990 nm, 950 nm, 900 nm, 850 nm, 800 nm, 750 nm, 720 nm, 700 nm, 680 nm, 650 nm, 600 nm 550 nm, or 500 nm.
- a lower limit of the thickness of the inorganic layer can be 20 nm, 30 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 150 nm, 200 nm, 250 nm, 280 nm, 300 nm, 350 nm, 380 nm, 400 nm, 430 nm, 450 nm, or 490 nm.
- the range of the thickness of the inorganic layer can be constituted by any of the upper limits and any of the lower limits.
- an upper limit of M1/M2 can be 7.5, 7.2, 7.0, 6.8, 6.5, 6.3, 6.0, 5.8, 5.5, 5.3, 5.0, 4.8, 4.5, 4.3, 4.0, 3.8, 3.5, 3.3, 3.1, or 3.0.
- a lower limit of M1/M2 can be 0.05, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, or 2.9.
- the range of M1/M2 can be constituted by any of the upper limits and any of the lower limits. If the value of M1/M2 is too small, the amount of the inorganic layer is small relative to the porous substrate and the coating is insufficient. When heated, the restriction against thermal shrinkage of the porous substrate by the inorganic layer is weak, and the inhibition effect against the thermal shrinkage of the separator is not significant while the composite membrane has low mechanical strength (such as small tensile strength, small puncture strength, etc.).
- the interfacial peeling force can be 30 N/m, 32 N/m, 34 N/m, 36 N/m, 38 N/m, 40 N/m, 42 N/m, 44 N/m, 46 N/m, etc.
- the separator is soaked in the electrolyte throughout the life cycle of the battery, and thus the interface between the coating layer and the porous substrate is deteriorated by acid/alkali corrosion in the electrolyte, resulting in decrease in the bonding force between the film layers.
- the bonding force between the porous inorganic dielectric layer and the substrate bonding force is smaller than 30 N/m, it means that bonding force is insufficient, and the porous inorganic dielectric layer readily falls off in the long term cycling or battery abuse situations, which not only causes the risk of blocking the pores of the substrate and reducing the ion conductivity of the battery, but also causes a series of safety problems.
- the thickness of the inorganic layer is 50 nm to 1500 nm, preferably 100 nm to 1000 nm, and more preferably 150 nm to 500 nm.
- the composite separator can be formed by using an ultra-thin inorganic layer and the porous substrate, and the formed composite separator not only has good wettability to electrolyte and almost no thermal shrinkage at 90° C., but also has good mechanical strength and high air permeability.
- the ultra-thin inorganic layer almost does not increase the thickness of the separator, which facilitates improving the energy density of the battery.
- the inorganic layer is in a porous structure, and a porosity of the inorganic layer is 10% ⁇ 60%, preferably 20% ⁇ 40%.
- An upper limit of the porosity can be 60%, 58%, 55%, 53%, 50%, 48%, 45%, 43%, 40%, 38%, or 35%
- a lower limit of the porosity can be 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, or 32%.
- the range of the porosity of the inorganic layer can be constituted by any of the upper limits and any of the lower limits.
- the porosity of the inorganic layer is too small, it will lead to a lower air permeability of the separator and thus adversely affect the ion transmission properties, resulting in poor dynamic performance of the battery. If the porosity of the inorganic layer is too large and the inorganic layer is too loose, it will adversely affect the mechanical properties of the separator, thereby reducing the reliability of battery in the long-term use.
- the porosity of the inorganic layer is measured in a manner as follows.
- a porous substrate is cut into two pieces of original substrate film samples with an identical area, one piece does not undergo any treatment, and the other piece is prepared with an inorganic layer.
- the two pieces are dried at 105° C. in a vacuum drying oven for 2 hours and then taken out and placed in a desiccator for cooling to be tested.
- each sample is wrapped evenly by an A4 paper, tiled on a cutting die, and punched by a punching machine, so that the sample is well prepared for testing.
- a tenthousandth micrometer is used to measure the thickness of the sample, and an apparent volume of the sample is calculated based on a surface area and the thickness of the sample.
- the apparent volumes of the bare porous substrate and the porous substrate prepared with the inorganic layer are denoted as V1 and V2, respectively.
- an AccuPyc II True Density Meter is used to measure true volume of the sample, and true volumes of the bare porous substrate and the porous substrate prepared with the inorganic layer are denoted as V3 and V4, respectively.
- the porosity of the inorganic layer can be calculated as [V2 ⁇ V4 ⁇ (V1 ⁇ V3)]/(V2 ⁇ V1)*100%.
- the inorganic layer is arranged on at least one surface of the substrate and at least a portion of inner walls of the pores of the substrate.
- the inorganic layer can cover the upper surface or the lower surface of the substrate and a portion of inner walls of the pores in the upper surface or lower surface; or the inorganic layer can cover both the upper and lower surfaces of the substrate and a portion of inner walls of the pores in the upper and lower surfaces of the substrate; or the inorganic layer can fully cover the upper and lower surfaces, and inner walls of the pores in the upper and lower surfaces of the substrate.
- a ratio of a depth of the inorganic layer in a pore of the substrate to the thickness of the substrate is d, and d is in a range of 1/1000 to 1/20, preferably 1/200 to 1/40.
- An upper limit of d can be 1/20, 1/22, 1/24, 1/26, 1/28, 1/30, 1/32, 1/35, 1/40, 1/50, 1/60, 1/70, 1/80, or 1/90; and a lower limit of d can be 1/1000, 1/900, 1/800, 1/700, 1/600, 1/500, 1/400, 1/300, 1/200, or 1/100.
- the range of d can be constituted by any of the upper limits and any of the lower limits.
- the ratio of the depth of inorganic layer in the pore of the substrate is related to the porosity of the substrate, the pore diameter, the process time used in preparing the inorganic layer, concentration of the vapor source, vapor flow rate, etc.
- the depth of the inorganic layer in the pore of the substrate is too large (e.g., larger than 1/20 of the thickness of the substrate)
- the periphery of the pores of the substrate will be easily blocked by the large amount of the inorganic layer, resulting in deterioration of the ion conduction performance of the electrochemical device.
- the depth of the inorganic layer in the pores of the substrate is too small (e.g., smaller than 1/1000 of the thickness of the substrate), there will be lots of polymer surfaces exposed in the pores. Therefore, when heated, since the interior of the substrate is subjected to almost no constraints of the inorganic layer, the improvement against the thermal shrinkage is not significant.
- the inorganic layer contains at least one of aluminum oxide, aluminum nitride, aluminum fluoride, silicon oxide, silicon nitride, silicon fluoride, titanium oxide, titanium nitride, titanium fluoride, zinc oxide, zinc nitride, zinc fluoride, magnesium oxide, magnesium fluoride, magnesium nitride, zirconium oxide, zirconium nitride, zirconium fluoride, calcium oxide, calcium fluoride, calcium nitride, barium oxide, barium fluoride, barium nitride, or AlO (OH).
- the substrate contains a material selected from a group consisting of polyethylene, polypropylene, polyvinylidene fluoride, aramid fiber, polyethylene glycol terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, natural fiber, or any combination thereof.
- porosity of the substrate is 20% ⁇ 80%, preferably 40% ⁇ 70%.
- An upper limit of the porosity of the substrate can be 80%, 78%, 75%, 73%, 70%, 68%, 65%, 63%, 60%, 58%, 55%, 53%, or 50%; and a lower limit of the porosity of the substrate can be 20%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 43%, 45%, or 48%.
- the range of the porosity of the substrate can be constituted by any of the upper limits and any of the lower limits.
- the inorganic layer could be deposited on the upper and lower surfaces and at least a portion of inner walls of the pores, in order to ensure that the separator has good ion conductivity performance, it is necessary to improve the porosity of the substrate, thereby ensuring pores of the substrate are not be blocked and avoiding the reduced dynamic performance of the battery.
- a pore diameter of the pore of the substrate is 0.01 ⁇ m to 0.5 ⁇ m, preferably 0.05 ⁇ m to 0.2 ⁇ m.
- An upper limit of the pore diameter can be 0.5 ⁇ m, 0.45 ⁇ m, 0.4 ⁇ m, 0.35 ⁇ m, 0.3 ⁇ m, 0.25 ⁇ m, 0.2 ⁇ m, or 0.15 ⁇ m; and a lower limit of the pore diameter can be 0.01 ⁇ m, 0.02 ⁇ m, 0.03 ⁇ m, 0.04 ⁇ m, 0.05 ⁇ m, 0.06 ⁇ m, 0.07 ⁇ m, 0.08 ⁇ m, 0.09 ⁇ m, or 0.1 ⁇ m.
- the range of the pore diameter can be constituted by any of the upper limits and any of the lower limits. Since the inorganic layer could be deposited on at least one surface of the substrate and at least a portion of inner walls of the pores in the surface, in order to ensure that the separator has good ion conductivity performance, it is necessary to improve the pore diameter of the substrate, thereby preventing the pores of the substrate from being blocked by the inorganic layer.
- the substrate has a thickness of 5 ⁇ m to 50 ⁇ m, preferably is 7 ⁇ m to 20 ⁇ m, more preferably 7 ⁇ m to 15 ⁇ m.
- An upper limit of the thickness of the substrate can be 50 ⁇ m, 48 ⁇ m, 45 ⁇ m, 43 ⁇ m, 40 ⁇ m, 38 ⁇ m, 35 ⁇ m, 33 ⁇ m, 30 ⁇ m, 28 ⁇ m, 25 ⁇ m, 23 ⁇ m, 22 ⁇ m, or 20 ⁇ m; and a lower limit of the thickness of the substrate can be 5 ⁇ m, 8 ⁇ m, 10 ⁇ m, 12 ⁇ m, 15 ⁇ m, or 18 ⁇ m.
- the range of the thickness of the substrate can be constituted by any of the upper limits and any of the lower limits.
- the air permeability of the separator is in range of 100 s ⁇ 280 s.
- An upper limit of the air permeability can be 280 s, 270s, 260 s, 250 s, 240 s, 230 s, 220 s, 210 s, 200 s, or 190 s; and a lower limit of the air permeability can be 100 s, 110, 120 s, 130 s, 140 s, 150 s, 160 s, 170 s, or 180 s.
- the range of the air permeability of the separator can be constituted by any of the upper limits and any of the lower limits.
- the air permeability (Gurley) of the separator is an important parameter for determining the ion conductivity of the separator.
- the inorganic layer is an ultra-thin film having a thickness of only tens of nanometers
- the inorganic layer is mainly deposited on the surface of the substrate and a portion of the inner walls of the pores.
- the pore diameter decreases as the thickness of the inorganic layer increases.
- the inorganic layer begins to form a continuous film layer on the surface of the substrate that covers the pores, and at this time, lithium-ions need to pass through the inorganic layer before entering into the substrate of the separator.
- the favorable ion conduction performance of the separator and the favorable dynamic and rate performances of the electrochemical device can be effectively ensured by regulating the relative contents of the inorganic layer and the substrate, the thickness and porosity of the inorganic layer, and the pore diameter and porosity of the substrate, controlling the air permeability to be in the range of 100 s-280 s.
- both a longitudinal thermal shrinkage percentage and a transverse thermal shrinkage percentage are lower than 3%, for example, 2.8%, 2.5%, 2%, 1.8%, 1.5%, 1.2%, 1%, 0.8%, 0.5%, 0.3%, etc.
- both the longitudinal thermal shrinkage percentage and the transverse thermal shrinkage percentage are lower than 2%, more preferably lower than 1%.
- a second aspect of the embodiments of the present disclosure provides a method for prepared the separator.
- the method includes at least steps of: providing a substrate, which is a porous substrate; and forming an inorganic layer on a surface of the substrate and in the pores by using vapor deposition method, so as to obtain the separator.
- the inorganic layer has a thickness of 20 nm to 2000 nm.
- a mass of the inorganic layer is M1, a mass of the substrate is M2, and a mass ratio of the inorganic layer to the substrate M1/M2 is greater than or equal to 0.05 but smaller than or equal to 7.5.
- An interfacial peeling force between the inorganic layer and the substrate is not smaller than 30 N/m.
- the inorganic layer not only can be deposited on the surface of the substrate, but also can be deposited on a portion of the inner walls of the pores in the substrate.
- the coating area percentage of the inorganic layer on the substrate increases, the inhibition effect against the thermal shrinkage of the substrate by the inorganic layer becomes more significant, and the tensile strength and puncture strength of the separator can be also increased, thereby effectively improving safety performance of the battery.
- the method further includes performing surface pretreatment on the substrate prior to forming the inorganic layer.
- the surface pretreatment includes one or more of plasma activation, corona pretreatment, chemical pretreatment, or electron beam pretreatment, and preferably, the surface pretreatment is plasma activation or electron beam pretreatment.
- high energy plasma or electron beam can be used to bombard the surface of the substrate. This can increase roughness of the substrate while activating function groups on the surface for increasing the deposition speed, and can modify micro morphology such as the porosity and pore diameter of the inorganic layer by adjusting process parameter during preparing the inorganic layer.
- the vapor deposition is a coating process selected from a group consisting of atomic layer deposition, chemical vapor deposition, physical vapor deposition, thermal evaporation, or any combination thereof.
- plasma assisted thermal evaporation deposition, reactive ion beam sputtering deposition, electron beam evaporation, magnetron sputtering method, or plasma arc plating method can be employed.
- the vapor deposition includes a step of forming the inorganic layer by reaction of a reactive gas and a gaseous precursor of the inorganic layer.
- the reactive gas is at least one of oxygen, ozone, carbon dioxide, water vapor, nitric oxide, nitrogen dioxide, or ammonia.
- the precursor of the inorganic layer is at least one of elementary aluminum, aluminum alloy, alkyl aluminum, aluminum nitrate, aluminum acetate, aluminum sulfate, elementary silicon, silicon alloy, alkyl silicon, silicon nitrate, silicon acetate, silicon sulfate, elementary titanium, titanium alloys, alkyl titanium, titanium nitrate, titanium acetate, titanium sulfate, elementary zinc, zinc alloy, alkyl zinc, zinc nitrate, zinc acetate, zinc sulfate, elementary magnesium, magnesium alloy, alkyl magnesium, magnesium nitrate, magnesium acetate, magnesium sulfate, elementary zirconium, zirconium alloy, alkyl zirconium, zirconium nitrate, zirconium acetate, zirconium sulfate, elementary calcium, calcium alloy, alkyl calcium, calcium nitrate, calcium acetate, calcium sulfate
- a third aspect of the embodiments of the present disclosure provides an electrochemical device.
- the electrochemical device includes a positive electrode, a negative electrode, a separator according to the first aspect of the embodiments of the present disclosure, and electrolyte.
- the electrochemical device of the embodiments of the present disclosure can be a lithium-ion secondary battery, a lithium primary battery, a sodium ion battery, or a magnesium ion battery, but is not limited herein.
- the lithium-ion secondary battery is taken as an example to further illustrate the embodiments of the present disclosure.
- the material of the substrate is not particularly limited, and can be a polymer that can be selected from a group consisting of polyethylene, polypropylene, ethylene-propylene copolymer, or any combination thereof.
- the plasma-assisted thermal evaporation deposition technology is taken as an example.
- a heating source is an electron beam
- a heating target material is an elementary substance except oxygen, such as Al, Si, Mg, or the like.
- an oxygen-containing active gas such as oxygen, ozone, oxygen ions, nitric oxide, nitrogen dioxide, carbon dioxide, water vapor, etc.
- temperature of the substrate is controlled to be lower than 100° C.
- deposition rate of the inorganic layer on the surface of the substrate can be adjusted, and further, a thickness, composition, and micro morphology of the inorganic layer can be adjusted.
- a positive electrode active material, a conductive agent of acetylene black (SP), and a binder of polyvinylidene fluoride (PVDF) are mixed at a weight ratio of 96:2:2.
- Solvent of N-methylpyrrolidone is added and then mixed and stirred evenly to obtain positive electrode slurry.
- the positive electrode slurry is evenly coated on the positive electrode current collector aluminum foil and then dried at 85° C. Thereafter, cold pressing, edge-cutting, slitting, and stripping are performed, followed by drying at 85° C. under vacuum for 4 hours, so that the positive electrode plate is obtained.
- the used positive electrode active material can be a layered lithium transition metal oxide, lithium-rich manganese oxide, lithium iron phosphate, lithium cobaltate, or a doped or coated positive electrode active material thereof.
- the layered lithium transition metal oxide LiNi 0.8 Co 0.1 Mn 0.1 O 2 is taken as an example.
- a negative electrode active material of artificial graphite, a conductive agent of acetylene black, a binder of styrene butadiene rubber (SBR) and a thickener of sodium carboxymethyl cellulose (CMC) are mixed with at weight ratio of 96:1:2:1.
- Solvent of deionized water is added and then mixed and stirred evenly to obtain negative electrode slurry.
- the negative electrode slurry is evenly coated on the negative electrode current collector copper foil and then dried at 80° C. to 90° C. Thereafter, cold pressing, edge-cutting, slitting, and stripping are performed, followed by drying at 110° C. under vacuum for 4 hours, so that the negative electrode plate is obtained.
- a basic electrolyte solution including dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) and ethylene carbonate (EC) with a weight ratio of 5:2:3 is prepared. Then electrolyte salt is added so that concentration of lithium hexafluorophosphate in the electrolyte solution is 1 mol/L.
- DMC dimethyl carbonate
- EMC ethyl methyl carbonate
- EC ethylene carbonate
- the negative electrode plate, the separator and the positive electrode plate are stacked in this order that the separator is placed between the positive electrode plate and the negative electrode plate and the surface of the separator with coating faces the positive electrode plate, and are wound to form a square bare cell with a thickness of 8 mm, a width of 60 mm, and a length of 130 mm.
- the bare cell is placed into an aluminum foil packing bag, and vacuum baked at 75° C. for 10 hours, and then, non-aqueous electrolyte is injected. After vacuum encapsulation is conducted, let it stand by for 24 hours.
- Lithium ion secondary batteries can be prepared by the above method. Specifically, the plasma-assisted thermal evaporation deposition is used to deposit an inorganic layer having certain parameters on the upper and lower surfaces of the porous substrate by vapor deposition method.
- the specific process parameters are illustrated as follows.
- the target material is metal aluminum (in which other element such as Si may be doped)
- the vacuum degree of the deposition chamber is smaller than 1 ⁇ 10 ⁇ 3 Pa
- the heating current is 190 A
- the oxygen flow rate is 300 sccm
- the plasma power is about 300 W
- the active reaction gas is oxygen
- the process time is 5 min.
- the composite separator was cut into a square sample of 100 mm in length and 100 mm in width, and marked with a longitudinal direction (MD) and a transverse direction (TD). After that, a projection tester was used to measure the lengths in the MD and TD directions and the lengths were recorded as L1 and L2. The separator was then placed in an air-circulating oven at 150° C. for one hour and then taken out. The projection tester was used again to measure the lengths in the MD and TD directions and these lengths were recorded as L3 and L4.
- MD longitudinal direction
- TD transverse direction
- Thermal shrinkage percentage of the separator in the MD direction ( L 1 ⁇ L 3)/ L 1 ⁇ 100%.
- Thermal shrinkage percentage of the separator in the TD direction ( L 2 ⁇ L 4)/ L 2 ⁇ 100%.
- the test sample with a fixed thickness of T was respectively die-cut along MD (length direction)/TD (width direction) using the cutting die to form sheets with a size of 100 mmx15 mm. Then, the sheet was placed to be perpendicular to a clamping chuck of the tensionmeter, and was fixed and tightened with upper and lower chucks with both initial heights of 5 cm. A tensile rate is set to be 50 mm/min, and the maximum pulling force measured is F.
- test sample Under a temperature of 15° C. to 28° C. and a humidity lower than 80%, the test sample was made into a size of 4 cm ⁇ 4 cm, and an air permeability value was directly obtained using an Air-permeability-tester with Gurley test (100 cc) method.
- test sample was placed on the water contact angle tester.
- a drop of deionized water was dropped on the test sample from a height of ⁇ 1 mm above the test sample, the water drop on the test sample was then photographed by an optical microscope and a high speed camera, and an inclined angle between a tangent line of the water drop to a contact point of the test sample was measured and analyzed by software.
- the battery In an incubator at 25° C., the battery was charged to a voltage of 4.2V at a constant current with a rate of 1 C, and then charged at a constant voltage of 4.2V to a current of 0.05 C. After that, it was discharged to a voltage of 2.8V at a constant current with a rate of 1 C, and in this way, the obtained discharge capacity was the capacity of the battery.
- the battery was charged to a voltage of 4.2V at a constant current with a rate of 0.7 C, and then it was charged with a constant voltage of 4.2V to a current of 0.05 C.
- a capacity retention rate after the 1000 cycles discharge capacity after the 1000 th cycle/discharge capacity after the first cycle ⁇ 100%.
- Each battery was charged to a voltage higher than 4.2V under a room temperature at a constant current with a rate of 0.3 C, and then charged with a constant voltage of 4.2V to a current lower than 0.05 C, so that the battery was in a fully charged state with a voltage of 4.2V.
- An internal pressure of the fully charged battery before storage was measured and denoted as P 0 .
- the fully charged battery was stored in an oven at 80° C. for 15 days, and then taken out and cooled for 1 hour, and subsequently, an internal pressure of the battery was measured and denoted as P n .
- the separator when the separator is not provided with the inorganic layer, the separator has high thermal shrinkage percentage and poor wettability, resulting in poor electrochemical performance (please refer to D1).
- the mass ratio of M1/M2 is too small, the amount of the inorganic layer relative to the amount of the porous substrate is small and the protected area of the substrate is low, and therefore, when heated, the inhibition effect against the thermal shrinkage of the separator by the inorganic layer is not significant while mechanical strength (such as tensile strength and puncture strength) of the composite separator is low (please refer to D2 and D4).
- the inorganic layer is too thick, M1/M2 is too large, the improvement effect for hydrophilicity, thermal shrinkage resistance, mechanical strength is not significant enhanced either, and with the increase of the thickness of the separator, the dynamic performance and energy density of the battery can be reduced instead (please refer to D3 and D5).
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Abstract
Description
- The present application claims priority to Chinese Patent Application No. 201711486159.9, filed on Dec. 29, 2017, the content of which is incorporated herein by reference in its entirety.
- The present disclosure relates to the field of energy storage and, in particular, relates to a separator, a method for preparing the separator and an electrochemical device containing the separator.
- In the internal structure of the battery, the separator, as a key component, is usually a porous polymer film, which has the characteristics of electron isolation and ion conduction, and is used for normal transmission of ions between a positive electrode and a negative electrode without short circuit. In recent years, in order to solve the problems of high thermal shrinkage and poor electrolyte wettability of a single polymer separator, a composite separator prepared by coating a ceramic coating layer on a surface of a polymer substrate has become a key technology to improve the safety performance of the battery. Forming an organic-inorganic composite coating layer by mixing inorganic particles and a binder can modify the surface of the polymer substrate. However, there are still some problems about such a composite separator that are needed for further research and development.
- For example, it is difficult to form a coating layer with a nano-scale thickness due to process constraints and requirements on technical effect. In addition, since bonding between the inorganic particles and the polymer substrate material is mainly achieved by the binder, bonding forces in different regions are significantly affected by the distribution of the binder. As a result, during the coating process, long-term cycling or battery abuse, the coating layer on the separator surface may easily occur cracks, aging, porosity changing, or detachment of ceramic particles and the like, thereby leading to deterioration of ion conduction performance and even cause security problems in severe cases.
- In view of this, a first aspect of the present disclosure provides a separator. The separator includes a substrate with a porous structure and an inorganic layer arranged on at least one side of the substrate. The substrate is a porous substrate having a plurality of pores. The inorganic layer is a dielectric layer containing no binder. A thickness of the inorganic layer is 20 nm to 2000 nm, a mass of the inorganic layer is M1, a mass of the substrate is M2, and a mass ratio of the inorganic layer to the substrate M1/M2 is greater than or equal to 0.05 but smaller than or equal to 7.5, and an interfacial peeling force between the inorganic layer and the substrate is not smaller than 30 N/m.
- A second aspect of the present disclosure provides a method for preparing the separator of the first aspect. The method includes at least steps of: providing a substrate, which is a porous substrate having a plurality of pores; and forming an inorganic layer on a surface of the substrate and in the pores by means of vapor deposition, so as to obtain the separator.
- A third aspect of the present disclosure provides an electrochemical device including a positive electrode, a negative electrode, a separator, and electrolyte. The separator is the separator of the first aspect.
- The technical solutions of the present disclosure have at least the following beneficial effects:
- By providing an ultra-thin inorganic layer containing no binder on the surface of the porous substrate, the interfacial wettability and thermal shrinkage resistance performance of the separator can be effectively improved while the separator has a certain mechanical strength. By controlling the mass ratio of M1/M2 and the value of the interfacial peeling force within a proper range, respectively, the separator can have favorable mechanical strength and thermal shrinkage percentage while having high energy density. In addition, since there is no binder between the substrate and the inorganic layer, the inorganic layer is prevented from cracking and falling-off caused by the uneven distribution of the binder, and the problems of decrease of mechanical strength and blockage of pores caused by the falling-off can be alleviated, thereby improving safety performance and cycling life of the battery.
- The present disclosure is further described with reference to embodiments and comparative examples. These embodiments are merely for illustrating the present disclosure rather than limiting the present disclosure. Any modification or equivalent replacement to the technical solutions of the present disclosure, without departing from the scope of the technical solutions of the present disclosure, shall fall into the protection scope of the application.
- First of all, a first aspect of the embodiments of the present disclosure provides a separator.
- The separator includes a substrate and an inorganic layer arranged on at least one side of the substrate. The substrate is a porous substrate having a plurality of pores. The inorganic layer is a dielectric layer containing no binder. The inorganic layer has a thickness of 20 nm to 2000 nm. A mass of the inorganic layer is M1, a mass of the substrate is M2, and a mass ratio of the inorganic layer to the substrate M1/M2 is greater than or equal to 0.05 but smaller than or equal to 7.5. An interfacial peeling force between the inorganic layer and the substrate is not smaller than 30 N/m.
- In the composite separator according to the first aspect of the embodiments of the present disclosure, since the ultra-thin inorganic layer is provided, the interfacial wettability and the thermal shrinkage resistance performance of the separator are effectively improved. When the mass ratio of M1/M2 is in the range of 0.05˜7.5, the separator has favorable mechanical strength and thermal shrinkage percentage while having high energy density. However, when a mass of the inorganic layer is further increased, the hydrophilicity to the separator, thermal shrinkage resistance performance and mechanical strength of the separator are not further significantly improved. Instead, it may reduce the porosity of the inorganic layer on the surface of the separator, increase the ion transmission distance, and affect the rapid transmission of ions between the positive and negative electrodes, thereby causing deterioration of the dynamic properties of the cell. In addition, since there is no binder between the substrate and the inorganic layer, the problems such as cracking and falling-off of the inorganic layer due to the uneven distribution of the binder can be avoided, and the problems of mechanical strength reduction and pore blocking of the substrate caused by the falling-off that deteriorates the ion conductivity of the battery can be also avoided. Therefore, the safety performance and the cycling life of the battery can be further improved.
- As an improvement to the separator of the embodiments of the disclosure, an upper limit of a thickness of the inorganic layer can be 2000 nm, 1900 nm, 1800 nm, 1700 nm, 1600 nm, 1500 nm, 1400 nm, 1300 nm, 1200 nm, 1100 nm, 1000 nm, 990 nm, 950 nm, 900 nm, 850 nm, 800 nm, 750 nm, 720 nm, 700 nm, 680 nm, 650 nm, 600 nm 550 nm, or 500 nm. A lower limit of the thickness of the inorganic layer can be 20 nm, 30 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, 70 nm, 80 nm, 90 nm, 100 nm, 110 nm, 150 nm, 200 nm, 250 nm, 280 nm, 300 nm, 350 nm, 380 nm, 400 nm, 430 nm, 450 nm, or 490 nm. The range of the thickness of the inorganic layer can be constituted by any of the upper limits and any of the lower limits.
- As an improvement to the separator of the embodiments of the disclosure, an upper limit of M1/M2 can be 7.5, 7.2, 7.0, 6.8, 6.5, 6.3, 6.0, 5.8, 5.5, 5.3, 5.0, 4.8, 4.5, 4.3, 4.0, 3.8, 3.5, 3.3, 3.1, or 3.0. A lower limit of M1/M2 can be 0.05, 0.09, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.0, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, or 2.9. The range of M1/M2 can be constituted by any of the upper limits and any of the lower limits. If the value of M1/M2 is too small, the amount of the inorganic layer is small relative to the porous substrate and the coating is insufficient. When heated, the restriction against thermal shrinkage of the porous substrate by the inorganic layer is weak, and the inhibition effect against the thermal shrinkage of the separator is not significant while the composite membrane has low mechanical strength (such as small tensile strength, small puncture strength, etc.). If the value of M1/M2 is too large, the improvements on hydrophilicity, thermal shrinkage resistance performance, and mechanical strength of the separator are not significant enhanced, and instead, the thickness of the separator can be increased, and the dynamic performance and energy density of the separator can be deteriorated.
- As an improvement of the separator of the embodiments of the disclosure, the interfacial peeling force can be 30 N/m, 32 N/m, 34 N/m, 36 N/m, 38 N/m, 40 N/m, 42 N/m, 44 N/m, 46 N/m, etc. The separator is soaked in the electrolyte throughout the life cycle of the battery, and thus the interface between the coating layer and the porous substrate is deteriorated by acid/alkali corrosion in the electrolyte, resulting in decrease in the bonding force between the film layers. If the bonding force between the porous inorganic dielectric layer and the substrate bonding force is smaller than 30 N/m, it means that bonding force is insufficient, and the porous inorganic dielectric layer readily falls off in the long term cycling or battery abuse situations, which not only causes the risk of blocking the pores of the substrate and reducing the ion conductivity of the battery, but also causes a series of safety problems.
- As an improvement to the separator of the embodiments of the disclosure, the thickness of the inorganic layer is 50 nm to 1500 nm, preferably 100 nm to 1000 nm, and more preferably 150 nm to 500 nm. In the above range, the composite separator can be formed by using an ultra-thin inorganic layer and the porous substrate, and the formed composite separator not only has good wettability to electrolyte and almost no thermal shrinkage at 90° C., but also has good mechanical strength and high air permeability. Compared with a porous substrate having a thickness of ten to tens of microns, the ultra-thin inorganic layer almost does not increase the thickness of the separator, which facilitates improving the energy density of the battery.
- As an improvement to the separator of the embodiments of the present disclosure, the inorganic layer is in a porous structure, and a porosity of the inorganic layer is 10%˜60%, preferably 20%˜40%. An upper limit of the porosity can be 60%, 58%, 55%, 53%, 50%, 48%, 45%, 43%, 40%, 38%, or 35%, and a lower limit of the porosity can be 10%, 13%, 15%, 18%, 20%, 23%, 25%, 28%, 30%, or 32%. The range of the porosity of the inorganic layer can be constituted by any of the upper limits and any of the lower limits. If the porosity of the inorganic layer is too small, it will lead to a lower air permeability of the separator and thus adversely affect the ion transmission properties, resulting in poor dynamic performance of the battery. If the porosity of the inorganic layer is too large and the inorganic layer is too loose, it will adversely affect the mechanical properties of the separator, thereby reducing the reliability of battery in the long-term use.
- The porosity of the inorganic layer is measured in a manner as follows. A porous substrate is cut into two pieces of original substrate film samples with an identical area, one piece does not undergo any treatment, and the other piece is prepared with an inorganic layer. The two pieces are dried at 105° C. in a vacuum drying oven for 2 hours and then taken out and placed in a desiccator for cooling to be tested. Then each sample is wrapped evenly by an A4 paper, tiled on a cutting die, and punched by a punching machine, so that the sample is well prepared for testing. Firstly, a tenthousandth micrometer is used to measure the thickness of the sample, and an apparent volume of the sample is calculated based on a surface area and the thickness of the sample. The apparent volumes of the bare porous substrate and the porous substrate prepared with the inorganic layer are denoted as V1 and V2, respectively. Then, an AccuPyc II True Density Meter is used to measure true volume of the sample, and true volumes of the bare porous substrate and the porous substrate prepared with the inorganic layer are denoted as V3 and V4, respectively. The porosity of the inorganic layer can be calculated as [V2−V4−(V1−V3)]/(V2−V1)*100%.
- As an improvement to the separator of the embodiments of the present disclosure, the inorganic layer is arranged on at least one surface of the substrate and at least a portion of inner walls of the pores of the substrate. Specifically, the inorganic layer can cover the upper surface or the lower surface of the substrate and a portion of inner walls of the pores in the upper surface or lower surface; or the inorganic layer can cover both the upper and lower surfaces of the substrate and a portion of inner walls of the pores in the upper and lower surfaces of the substrate; or the inorganic layer can fully cover the upper and lower surfaces, and inner walls of the pores in the upper and lower surfaces of the substrate.
- As an improvement to the separator of the embodiments of the disclosure, a ratio of a depth of the inorganic layer in a pore of the substrate to the thickness of the substrate is d, and d is in a range of 1/1000 to 1/20, preferably 1/200 to 1/40. An upper limit of d can be 1/20, 1/22, 1/24, 1/26, 1/28, 1/30, 1/32, 1/35, 1/40, 1/50, 1/60, 1/70, 1/80, or 1/90; and a lower limit of d can be 1/1000, 1/900, 1/800, 1/700, 1/600, 1/500, 1/400, 1/300, 1/200, or 1/100. The range of d can be constituted by any of the upper limits and any of the lower limits. The ratio of the depth of inorganic layer in the pore of the substrate is related to the porosity of the substrate, the pore diameter, the process time used in preparing the inorganic layer, concentration of the vapor source, vapor flow rate, etc. When the depth of the inorganic layer in the pore of the substrate is too large (e.g., larger than 1/20 of the thickness of the substrate), the periphery of the pores of the substrate will be easily blocked by the large amount of the inorganic layer, resulting in deterioration of the ion conduction performance of the electrochemical device. If the depth of the inorganic layer in the pores of the substrate is too small (e.g., smaller than 1/1000 of the thickness of the substrate), there will be lots of polymer surfaces exposed in the pores. Therefore, when heated, since the interior of the substrate is subjected to almost no constraints of the inorganic layer, the improvement against the thermal shrinkage is not significant.
- As an improvement to the separator of the embodiments of the present disclosure, the inorganic layer contains at least one of aluminum oxide, aluminum nitride, aluminum fluoride, silicon oxide, silicon nitride, silicon fluoride, titanium oxide, titanium nitride, titanium fluoride, zinc oxide, zinc nitride, zinc fluoride, magnesium oxide, magnesium fluoride, magnesium nitride, zirconium oxide, zirconium nitride, zirconium fluoride, calcium oxide, calcium fluoride, calcium nitride, barium oxide, barium fluoride, barium nitride, or AlO (OH).
- As an improvement to the separator of the embodiments of the present disclosure, the substrate contains a material selected from a group consisting of polyethylene, polypropylene, polyvinylidene fluoride, aramid fiber, polyethylene glycol terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, natural fiber, or any combination thereof.
- As an improvement to the separator of the embodiments of the present disclosure, porosity of the substrate is 20%˜80%, preferably 40%˜70%. An upper limit of the porosity of the substrate can be 80%, 78%, 75%, 73%, 70%, 68%, 65%, 63%, 60%, 58%, 55%, 53%, or 50%; and a lower limit of the porosity of the substrate can be 20%, 25%, 28%, 30%, 32%, 35%, 38%, 40%, 43%, 45%, or 48%. The range of the porosity of the substrate can be constituted by any of the upper limits and any of the lower limits. Since the inorganic layer could be deposited on the upper and lower surfaces and at least a portion of inner walls of the pores, in order to ensure that the separator has good ion conductivity performance, it is necessary to improve the porosity of the substrate, thereby ensuring pores of the substrate are not be blocked and avoiding the reduced dynamic performance of the battery.
- As an improvement to the separator of the embodiments of the present disclosure, a pore diameter of the pore of the substrate is 0.01 μm to 0.5 μm, preferably 0.05 μm to 0.2 μm. An upper limit of the pore diameter can be 0.5 μm, 0.45 μm, 0.4 μm, 0.35 μm, 0.3 μm, 0.25 μm, 0.2 μm, or 0.15 μm; and a lower limit of the pore diameter can be 0.01 μm, 0.02 μm, 0.03 μm, 0.04 μm, 0.05 μm, 0.06 μm, 0.07 μm, 0.08 μm, 0.09 μm, or 0.1 μm. The range of the pore diameter can be constituted by any of the upper limits and any of the lower limits. Since the inorganic layer could be deposited on at least one surface of the substrate and at least a portion of inner walls of the pores in the surface, in order to ensure that the separator has good ion conductivity performance, it is necessary to improve the pore diameter of the substrate, thereby preventing the pores of the substrate from being blocked by the inorganic layer.
- As an improvement to the separator of the embodiments of the present disclosure, the substrate has a thickness of 5 μm to 50 μm, preferably is 7 μm to 20 μm, more preferably 7 μm to 15 μm. An upper limit of the thickness of the substrate can be 50 μm, 48 μm, 45 μm, 43 μm, 40 μm, 38 μm, 35 μm, 33 μm, 30 μm, 28 μm, 25 μm, 23 μm, 22 μm, or 20 μm; and a lower limit of the thickness of the substrate can be 5 μm, 8 μm, 10 μm, 12 μm, 15 μm, or 18 μm. The range of the thickness of the substrate can be constituted by any of the upper limits and any of the lower limits.
- As an improvement to the separator of the embodiments of the present disclosure, the air permeability of the separator is in range of 100 s˜280 s. An upper limit of the air permeability can be 280 s, 270s, 260 s, 250 s, 240 s, 230 s, 220 s, 210 s, 200 s, or 190 s; and a lower limit of the air permeability can be 100 s, 110, 120 s, 130 s, 140 s, 150 s, 160 s, 170 s, or 180 s. The range of the air permeability of the separator can be constituted by any of the upper limits and any of the lower limits.
- The air permeability (Gurley) of the separator is an important parameter for determining the ion conductivity of the separator. When the inorganic layer is an ultra-thin film having a thickness of only tens of nanometers, the inorganic layer is mainly deposited on the surface of the substrate and a portion of the inner walls of the pores. The pore diameter decreases as the thickness of the inorganic layer increases. With the gradual increase of the thickness of the inorganic layer, the inorganic layer begins to form a continuous film layer on the surface of the substrate that covers the pores, and at this time, lithium-ions need to pass through the inorganic layer before entering into the substrate of the separator. In the embodiments of the present disclosure, the favorable ion conduction performance of the separator and the favorable dynamic and rate performances of the electrochemical device can be effectively ensured by regulating the relative contents of the inorganic layer and the substrate, the thickness and porosity of the inorganic layer, and the pore diameter and porosity of the substrate, controlling the air permeability to be in the range of 100 s-280 s.
- As an improvement to the separator of the embodiments of the present disclosure, when the separator is separately placed at 90° C. for one hour, both a longitudinal thermal shrinkage percentage and a transverse thermal shrinkage percentage are lower than 3%, for example, 2.8%, 2.5%, 2%, 1.8%, 1.5%, 1.2%, 1%, 0.8%, 0.5%, 0.3%, etc. Preferably, both the longitudinal thermal shrinkage percentage and the transverse thermal shrinkage percentage are lower than 2%, more preferably lower than 1%.
- A second aspect of the embodiments of the present disclosure provides a method for prepared the separator. The method includes at least steps of: providing a substrate, which is a porous substrate; and forming an inorganic layer on a surface of the substrate and in the pores by using vapor deposition method, so as to obtain the separator. The inorganic layer has a thickness of 20 nm to 2000 nm. A mass of the inorganic layer is M1, a mass of the substrate is M2, and a mass ratio of the inorganic layer to the substrate M1/M2 is greater than or equal to 0.05 but smaller than or equal to 7.5. An interfacial peeling force between the inorganic layer and the substrate is not smaller than 30 N/m.
- By using the vapor deposition method to form the inorganic layer, the inorganic layer not only can be deposited on the surface of the substrate, but also can be deposited on a portion of the inner walls of the pores in the substrate. As the coating area percentage of the inorganic layer on the substrate increases, the inhibition effect against the thermal shrinkage of the substrate by the inorganic layer becomes more significant, and the tensile strength and puncture strength of the separator can be also increased, thereby effectively improving safety performance of the battery. Since no binder is used, the problems of cracks and fall-off of the inorganic layer caused by the uneven distribution of the binder can be avoided, therefore the decrease of mechanical strength and blocking pores of the substrate caused by the fall-off can be also avoided, thereby enhancing the ion conductivity of the separator and further improving safety performance of the battery and extending the cycle life of the battery.
- As an improvement to the method for preparing the separator of the embodiments of the present disclosure, the method further includes performing surface pretreatment on the substrate prior to forming the inorganic layer. The surface pretreatment includes one or more of plasma activation, corona pretreatment, chemical pretreatment, or electron beam pretreatment, and preferably, the surface pretreatment is plasma activation or electron beam pretreatment. Prior to the deposition of the inorganic layer, high energy plasma or electron beam can be used to bombard the surface of the substrate. This can increase roughness of the substrate while activating function groups on the surface for increasing the deposition speed, and can modify micro morphology such as the porosity and pore diameter of the inorganic layer by adjusting process parameter during preparing the inorganic layer.
- As an improvement to the method for preparing the separator of the embodiments of the present disclosure, the vapor deposition is a coating process selected from a group consisting of atomic layer deposition, chemical vapor deposition, physical vapor deposition, thermal evaporation, or any combination thereof. Preferably, plasma assisted thermal evaporation deposition, reactive ion beam sputtering deposition, electron beam evaporation, magnetron sputtering method, or plasma arc plating method can be employed.
- As an improvement to the method for preparing the separator of the embodiments of the present disclosure, the vapor deposition includes a step of forming the inorganic layer by reaction of a reactive gas and a gaseous precursor of the inorganic layer.
- As an improvement to the method for preparing the separator of the embodiments of the present disclosure, the reactive gas is at least one of oxygen, ozone, carbon dioxide, water vapor, nitric oxide, nitrogen dioxide, or ammonia.
- As an improvement to the method for preparing the separator of the embodiments of the present disclosure, the precursor of the inorganic layer is at least one of elementary aluminum, aluminum alloy, alkyl aluminum, aluminum nitrate, aluminum acetate, aluminum sulfate, elementary silicon, silicon alloy, alkyl silicon, silicon nitrate, silicon acetate, silicon sulfate, elementary titanium, titanium alloys, alkyl titanium, titanium nitrate, titanium acetate, titanium sulfate, elementary zinc, zinc alloy, alkyl zinc, zinc nitrate, zinc acetate, zinc sulfate, elementary magnesium, magnesium alloy, alkyl magnesium, magnesium nitrate, magnesium acetate, magnesium sulfate, elementary zirconium, zirconium alloy, alkyl zirconium, zirconium nitrate, zirconium acetate, zirconium sulfate, elementary calcium, calcium alloy, alkyl calcium, calcium nitrate, calcium acetate, calcium sulfate, elementary barium, barium alloy, alkyl barium, barium nitrate, barium acetate, or barium sulfate.
- A third aspect of the embodiments of the present disclosure provides an electrochemical device. The electrochemical device includes a positive electrode, a negative electrode, a separator according to the first aspect of the embodiments of the present disclosure, and electrolyte. The electrochemical device of the embodiments of the present disclosure can be a lithium-ion secondary battery, a lithium primary battery, a sodium ion battery, or a magnesium ion battery, but is not limited herein.
- The lithium-ion secondary battery is taken as an example to further illustrate the embodiments of the present disclosure.
- Separator
- In the embodiments of the present disclosure, the material of the substrate is not particularly limited, and can be a polymer that can be selected from a group consisting of polyethylene, polypropylene, ethylene-propylene copolymer, or any combination thereof.
- As for the method for preparing the inorganic layer of the separator, the plasma-assisted thermal evaporation deposition technology is taken as an example. A heating source is an electron beam, and a heating target material is an elementary substance except oxygen, such as Al, Si, Mg, or the like. Under vacuum conditions, an oxygen-containing active gas (such as oxygen, ozone, oxygen ions, nitric oxide, nitrogen dioxide, carbon dioxide, water vapor, etc.) is used as a reaction gas, and temperature of the substrate is controlled to be lower than 100° C. By adjusting current for heating and evaporation (10 A to 300 A), vacuum degree of a process chamber (10−1 Pa to 10−3 Pa), oxygen flow rate (100 sccm to 2000 sccm), plasma power (300 W to 600 W) and process time, deposition rate of the inorganic layer on the surface of the substrate can be adjusted, and further, a thickness, composition, and micro morphology of the inorganic layer can be adjusted.
- Preparation of Positive Electrode Plate
- A positive electrode active material, a conductive agent of acetylene black (SP), and a binder of polyvinylidene fluoride (PVDF) are mixed at a weight ratio of 96:2:2. Solvent of N-methylpyrrolidone is added and then mixed and stirred evenly to obtain positive electrode slurry. The positive electrode slurry is evenly coated on the positive electrode current collector aluminum foil and then dried at 85° C. Thereafter, cold pressing, edge-cutting, slitting, and stripping are performed, followed by drying at 85° C. under vacuum for 4 hours, so that the positive electrode plate is obtained. Additionally, the used positive electrode active material can be a layered lithium transition metal oxide, lithium-rich manganese oxide, lithium iron phosphate, lithium cobaltate, or a doped or coated positive electrode active material thereof. In this embodiment, the layered lithium transition metal oxide LiNi0.8Co0.1Mn0.1O2 is taken as an example.
- Preparation of Negative Electrode Plate
- A negative electrode active material of artificial graphite, a conductive agent of acetylene black, a binder of styrene butadiene rubber (SBR) and a thickener of sodium carboxymethyl cellulose (CMC) are mixed with at weight ratio of 96:1:2:1. Solvent of deionized water is added and then mixed and stirred evenly to obtain negative electrode slurry. The negative electrode slurry is evenly coated on the negative electrode current collector copper foil and then dried at 80° C. to 90° C. Thereafter, cold pressing, edge-cutting, slitting, and stripping are performed, followed by drying at 110° C. under vacuum for 4 hours, so that the negative electrode plate is obtained.
- Preparation of Electrolyte
- A basic electrolyte solution including dimethyl carbonate (DMC), ethyl methyl carbonate (EMC) and ethylene carbonate (EC) with a weight ratio of 5:2:3 is prepared. Then electrolyte salt is added so that concentration of lithium hexafluorophosphate in the electrolyte solution is 1 mol/L.
- Preparation of Lithium Ion Battery
- The negative electrode plate, the separator and the positive electrode plate are stacked in this order that the separator is placed between the positive electrode plate and the negative electrode plate and the surface of the separator with coating faces the positive electrode plate, and are wound to form a square bare cell with a thickness of 8 mm, a width of 60 mm, and a length of 130 mm. The bare cell is placed into an aluminum foil packing bag, and vacuum baked at 75° C. for 10 hours, and then, non-aqueous electrolyte is injected. After vacuum encapsulation is conducted, let it stand by for 24 hours. Then, it is charged to 4.2V with a constant current of 0.1 C (160 mA), and after that, it is charged at a constant voltage of 4.2V until the current drops to 0.05 C (80 mA). Then it is discharged to 3.0V with the constant current of 0.1 C (160 mA). After the charge-discharge is repeated for two times, it is charged to 3.8V with the constant current of 0.1 C (160 mA). In this way, preparation of the lithium-ion secondary battery is completed.
- Lithium ion secondary batteries can be prepared by the above method. Specifically, the plasma-assisted thermal evaporation deposition is used to deposit an inorganic layer having certain parameters on the upper and lower surfaces of the porous substrate by vapor deposition method.
- The specific process parameters are illustrated as follows. The target material is metal aluminum (in which other element such as Si may be doped), the vacuum degree of the deposition chamber is smaller than 1×10 −3 Pa, the heating current is 190 A, the oxygen flow rate is 300 sccm, the plasma power is about 300 W, the active reaction gas is oxygen, and the process time is 5 min.
- Specific parameters of the prepared separators are shown in Table 1.
-
TABLE 1 Inorganic Layer Substrate Thickness Thickness Pore diameter No. nm Porosity μm μm Porosity M1/M2 d Separator 1 20 20% 15 0.06 40% 0.07 1/800 Separator 2 50 15% 10 0.05 45% 0.30 1/500 Separator 3 100 20% 15 0.07 45% 0.38 1/420 Separator 4 200 25% 12 0.06 40% 0.81 1/210 Separator 5 300 30% 18 0.06 45% 0.82 1/111 Separator 6 500 35% 13 0.08 50% 1.26 1/85 Separator 7 800 40% 15 0.07 45% 1.35 1/63 Separator 8 1000 38% 18 0.06 40% 2.22 1/50 Separator 9 1500 40% 20 0.06 50% 3.48 1/40 Separator 10 2000 35% 13 0.06 40% 6.45 1/25 Separator 11 500 5% 15 0.06 50% 2.45 1/80 Separator 12 500 20% 15 0.07 55% 4.13 1/83 Separator 13 500 60% 10 0.08 50% 1.03 1/80 Separator 14 500 70% 15 0.10 55% 0.86 1/84 Separator 15 500 38% 5 0.06 45% 4.36 1/20 Separator 16 500 30% 30 0.10 60% 1.13 1/150 Separator 17 500 30% 45 0.06 50% 0.60 1/300 Separator 18 500 30% 55 0.15 60% 0.62 1/700 Separator 19 500 30% 20 0.07 60% 1.69 1/60 Separator 20 500 30% 20 0.06 20% 0.85 1/150 Separator 21 500 30% 20 0.05 80% 3.39 1/30 Separator D1 — — 18 0.06 40% — — Separator D2 8 15% 20 0.05 42% 0.02 1/5000 Separator D3 2250 40% 13 0.06 50% 8.04 1/59 Separator D4 20 30% 50 0.06 55% 0.02 1/3000 Separator D5 2000 32% 5 0.05 40% 17.55 — In Table 1, “—” indicates that the corresponding layer is absent. - Test procedures and test results of the separators and the lithium-ion secondary batteries will be described in detail below.
- (1) Interfacial Peeling Force Test
- Under room temperature and normal pressure conditions, 3M double-sided adhesive was evenly attached to a stainless steel plate, and then a test sample was evenly attached to the double-sided adhesive in a width of 2 cm. The sample was peeled from the steel plate by using a tensionmeter. The maximum pulling force F (N) was read according to a data chart of the pulling force and the displacement. The measured force was F/0.02.
- (2) Test for Thermal Shrinkage Percentage of the Separator
- The composite separator was cut into a square sample of 100 mm in length and 100 mm in width, and marked with a longitudinal direction (MD) and a transverse direction (TD). After that, a projection tester was used to measure the lengths in the MD and TD directions and the lengths were recorded as L1 and L2. The separator was then placed in an air-circulating oven at 150° C. for one hour and then taken out. The projection tester was used again to measure the lengths in the MD and TD directions and these lengths were recorded as L3 and L4.
-
Thermal shrinkage percentage of the separator in the MD direction=(L1−L3)/L1×100%. -
Thermal shrinkage percentage of the separator in the TD direction=(L2−L4)/L2×100%. - (3) Test for Tensile Strength of the Separator
- The test sample with a fixed thickness of T was respectively die-cut along MD (length direction)/TD (width direction) using the cutting die to form sheets with a size of 100 mmx15 mm. Then, the sheet was placed to be perpendicular to a clamping chuck of the tensionmeter, and was fixed and tightened with upper and lower chucks with both initial heights of 5 cm. A tensile rate is set to be 50 mm/min, and the maximum pulling force measured is F.
-
Tensile strength=F/9.8/(15 mm×T) - (4) Test for Air Permeability of the Separator
- Under a temperature of 15° C. to 28° C. and a humidity lower than 80%, the test sample was made into a size of 4 cm×4 cm, and an air permeability value was directly obtained using an Air-permeability-tester with Gurley test (100 cc) method.
- (5) Test for Wettability of Separator
- The test sample was placed on the water contact angle tester. A drop of deionized water was dropped on the test sample from a height of ≤1 mm above the test sample, the water drop on the test sample was then photographed by an optical microscope and a high speed camera, and an inclined angle between a tangent line of the water drop to a contact point of the test sample was measured and analyzed by software.
- The tested results of physical properties of the separators are shown in Table 2.
- (6) Test for Capacity of the Lithium-Ion Secondary Battery
- In an incubator at 25° C., the battery was charged to a voltage of 4.2V at a constant current with a rate of 1 C, and then charged at a constant voltage of 4.2V to a current of 0.05 C. After that, it was discharged to a voltage of 2.8V at a constant current with a rate of 1 C, and in this way, the obtained discharge capacity was the capacity of the battery.
- (7) Test for Cycling Performance at Ambient Temperature of the Lithium-Ion Secondary Battery
- At 25° C., the battery was charged to a voltage of 4.2V at a constant current with a rate of 0.7 C, and then it was charged with a constant voltage of 4.2V to a current of 0.05 C.
- After that, it was discharged at a constant current of 1 C to a voltage of 2.8V. This is a charge-discharge cycle process, and this charge-discharge cycle process was repeated 1000 times.
- A capacity retention rate after the 1000 cycles=discharge capacity after the 1000th cycle/discharge capacity after the first cycle×100%.
- (8) Test for High Temperature Storage and Gas Generation
- Five batteries were selected respectively from the batteries of each embodiment and each comparative example. Each battery was charged to a voltage higher than 4.2V under a room temperature at a constant current with a rate of 0.3 C, and then charged with a constant voltage of 4.2V to a current lower than 0.05 C, so that the battery was in a fully charged state with a voltage of 4.2V. An internal pressure of the fully charged battery before storage was measured and denoted as P0. The fully charged battery was stored in an oven at 80° C. for 15 days, and then taken out and cooled for 1 hour, and subsequently, an internal pressure of the battery was measured and denoted as Pn.
- A pressure change value of the battery before and after storage was calculated according to the formula: ΔP=Pn−P0.
- The test results of the electrochemical properties of the lithium ion secondary batteries prepared by using the above separators are specifically shown in Table 3.
-
TABLE 2 Physical properties of separators Thermal Shrinkage Tensile Strength Interfacial Percentage MD TD Air Peeling MD TD direction direction Permeability Wettability No. Force (N) (%) (%) (kgf/cm2) (kgf/cm2) (s) (°) Separator 1 34 1.56 0.19 1268 1349 112 50 Separator 2 34 1.43 −0.12 1372 1368 128 40 Separator 3 39 0.98 −0.09 1221 1258 126 20 Separator 4 39 0.96 −0.13 1306 1333 133 15 Separator 5 37 0.63 −0.11 1341 1241 132 0 Separator 6 35 0.61 −0.08 1330 1293 147 0 Separator 7 32 0.56 0.20 1330 1389 186 0 Separator 8 33 0.48 −0.18 1324 1209 180 0 Separator 9 34 0.50 0.01 1366 1277 183 0 Separator 10 32 0.61 0.07 1264 1388 188 0 Separator 11 39 0.49 −0.12 1398 1311 281 0 Separator 12 31 0.61 −0.09 1226 1368 183 0 Separator 13 35 0.51 0.02 1389 1365 130 0 Separator 14 34 0.53 −0.08 1363 1345 122 0 Separator 15 31 0.52 −0.01 1311 1398 188 0 Separator 16 38 0.53 −0.03 1271 1203 180 0 Separator 17 32 0.85 0.05 1292 1249 187 0 Separator 18 33 0.58 0.10 1308 1280 186 0 Separator 19 37 0.49 0.20 1232 1387 183 0 Separator 20 34 0.54 0.07 1254 1229 290 0 Separator 21 38 0.43 −0.14 1272 1335 188 0 Separator D1 — 2.30 0.40 1049 1119 92 120 Separator D2 35 2.34 0.05 1138 1112 112 65 Separator D3 25 0.51 0.02 1289 1365 320 0 Separator D4 33 2.20 0.37 1305 1373 180 55 Separator D5 40 0.21 0.05 1150 1204 350 0 -
TABLE 3 Electrochemical properties of separators Capacity Average Battery Retention Rate Pressure Capacity after 1000 Change No. (mAh) Cycles (%) (MPa) Battery 1 Separator 1 1697 90.90% 0.446 Battery 2 Separator 2 1690 89.30% 0.321 Battery 3 Separator 3 1684 89.20% 0.222 Battery 4 Separator 4 1680 90.20% 0.172 Battery 5 Separator 5 1681 91.10% 0.141 Battery 6 Separator 6 1663 92.90% 0.211 Battery 7 Separator 7 1645 90.50% 0.216 Battery 8 Separator 8 1654 90.10% 0.172 Battery 9 Separator 9 1658 90.90% 0.521 Battery 10 Separator 10 1656 88.50% 0.129 Battery 11 Separator 11 1668 88.16% 0.121 Battery 12 Separator 12 1663 90.21% 0.138 Battery 13 Separator 13 1668 90.30% 0.159 Battery 14 Separator 14 1663 90.92% 0.230 Battery 15 Separator 15 1689 90.24% 0.137 Battery 16 Separator 16 1654 90.52% 0.155 Battery 17 Separator 17 1638 91.00% 0.146 Battery 18 Separator 18 1601 91.20% 0.145 Battery 19 Separator 19 1651 91.06% 0.140 Battery 20 Separator 20 1648 88.24% 0.120 Battery 21 Separator 21 1643 90.37% 0.121 Battery D1 Separator D1 1662 87.81% 0.514 Battery D2 Separator D2 1622 88.82% 0.508 Battery D3 Separator D3 1608 88.30% 0.149 Battery D4 Separator D4 1610 90.10% 0.432 Battery D5 Separator D5 1640 87.40% 0.211 - It can be seen from the above embodiments and comparative examples that when the separator is not provided with the inorganic layer, the separator has high thermal shrinkage percentage and poor wettability, resulting in poor electrochemical performance (please refer to D1). When the mass ratio of M1/M2 is too small, the amount of the inorganic layer relative to the amount of the porous substrate is small and the protected area of the substrate is low, and therefore, when heated, the inhibition effect against the thermal shrinkage of the separator by the inorganic layer is not significant while mechanical strength (such as tensile strength and puncture strength) of the composite separator is low (please refer to D2 and D4). If the inorganic layer is too thick, M1/M2 is too large, the improvement effect for hydrophilicity, thermal shrinkage resistance, mechanical strength is not significant enhanced either, and with the increase of the thickness of the separator, the dynamic performance and energy density of the battery can be reduced instead (please refer to D3 and D5).
- Although the present disclosure is disclosed with the preferred embodiments above, these embodiments are not intended to limit the claims, and any person skilled in the art may make several possible changes and modifications without departing from the conception of the present disclosure. Therefore, the protection scope of the present disclosure should be defined by the scope of the claims of the present disclosure.
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US2673230A (en) * | 1949-01-08 | 1954-03-23 | Joseph B Brennan | Battery separator |
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